Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/50—Reversal development; Contact processes

Definitions

• This invention relates to photography, and more particularly, to photographic developers for use in reversal processing of photographic color films and papers.
• multi-layer photographic elements used for color photography there are usually at least three selectively sensitive emulsion layers coated on a conventional photographic support, such as cellulose ester film, paper, polyvinyl resin film, polyester film, etc.
• a conventional photographic support such as cellulose ester film, paper, polyvinyl resin film, polyester film, etc.
• the uppermost silver halide emulsion layer may be bluesensitive, while the silver halide emulsion layer closest to the support may be red-sensitized.
• a green sensitized silver halide emulsion layer there may be a green sensitized silver halide emulsion layer.
• a yellow filter layer is used between the blue-sensitive and the green-sensitized silver halide emulsion layer.
• additional silver halide emulsion layers, gelatin interlayers, and the like may also be present.
• the silver halide emulsion layers may contain some of the processing ingredients, such as the color-forming compounds or couplers.
• the photographic material is first processed to a conventional black-and-white silver negative in a developer which does not contain a developing agent capable of coupling with any of the color-forming compounds or couplers which may be present. Without removing unexposed silver halide, the material is given a reversal reexposure, followed by color development.
• the technique of color reversal processing is well known to those skilled in the photographic art and color materials which can be used in such processing have been previously described in a number of domestic and foreign patents, such as Mannes et al. US. Patent 2,252,718, issued August 19, 1941.
• the color materials useful in the present invention include those having silver halide emulsion layers containing the color-forming materials or couplers in a layer, or layers, as well as color materials intended for processing in a color developer which contains the color coupler.
• cyclohexane compounds containing an amino radical and in addition to the amino radical, a polar substituent, such as hydroxyl, amino, hydroxyalkyl (hydroxyethyl, hydroxypropyl, etc.), etc.
• Particularly useful cyclohexane compounds are those which contain an aminomethyl substituent.
• Typical cyclohexane compounds useful in our invention comprise 1,4-bis(methylamino)cyclohexane, 4- aminocyclohexanol, 1-cyclohexaneamino-Z-propanol, etc.
• cyclohexane compounds of our invention when used either in the black-and-white negative developer, or in one or more of the color developers, have adequate photographic activity and permit reasonable film speeds with very low fog density. They have low volatility, low toxicity, high water solubility and only a slight tendency to form carbamates under the alkaline conditions present in many of these photographic developers. In addition, when these cyclohexane compounds are employed in color developers, they show no tendency to reduce the sharpness of the color images.
• the cyclohexane compounds used as silver halide solvents in our invention can be employed under rather wide concentration ranges, depending upon the type of silver halide developer, concentration of alkali, type of alkali, type of coupler, etc. In general, we have found that quite useful results are obtained in black-and-white silver halide negative developers if the concentration of the cyclohexane compound varies from about 0.5 to 10 grams per liter. Approximately the same concentration ranges for the cyclohexane compound can be employed in color developers, although we have found that especially good results are obtained within the range of about 1 to 8 grams per liter.
• the cyclohexane compounds of our invention can be employed in a variety of aqueous alkaline solutions containing various photographic developing agents.
• the black-and-white negative developing agents which have been found particularly useful in our invention comprise the dihydroxybenzenes, such as hydroquinone, toluquinone, etc., N-methyl-p-aminophenol salts, etc., or mixtures of such developing agents.
• useful in the negative developers of our invention are the 3-pyrazolidones, such as 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1- phenyl-3-pyrazolidone, etc.
• Typical of r-forrning developers are the sulfonarnido substituted penylenediamines disclosed in Weissberger et al., US. Pa nt 2,548,574, issued April 10, 195]; the substituted p-p enylenediamines disclosed in Weissberger et al., US. Patent 2,566,271, issued August 28, 1951, etc.
• the pH of the developers useful in our process can vary depending upon the particularv photographic material which is to be processed in the developers.
• color developers it has been found that the cyclohexane compounds of our invention are outstanding at relatively high pH values, i.e., where the pH is at least 10.0 and as high as 11.5 to 12.5.
• Our invention is primarily directed to the development of the ordinarily employed gelatino-silver-balide developing-out emulsions, e.g., gelatino-silver-chloride, -chlorobromide, -chioroiodide, -chiorobromiodide, -bromide, -bromiodide, etc. While the results illustrated below were obtained using gelatino-silver bromiodide emulsions, excellent results can be obtained using other silver halide emulsions. These emulsions can be coated in the usual manner on a suitable support, e.g.. glass, cellulose nitrate film, cellulose acetate film, polyvinyl film, polyester film, paper, metal, etc.
• a suitable support e.g. glass, cellulose nitrate film, cellulose acetate film, polyvinyl film, polyester film, paper, metal, etc.
• Photographic silver halide emulsions useful in our iuverition can also contain such addenda as chemical sensitizers, e.g.. sulfur sensitizers (e.g., allyl thiocarbarnide, thiourea. allyl isothiocyanate, cystine, etc), various gold compounds (eg. potassium chloroaurate, auric trichloride, etc.) (see US. Patents 2,540,085; 2,597,856 and 2,597,915), various azaindene compounds (such as those disclosed in US. Patent 2,716,062), condensation prodcol nets of alkylene oxides, such as those shown in US. Patent 2,400,532, as well as the additives mentioned in Jones et al.,'U.S. Patent 2,937,089.
• chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbarnide, thiourea. allyl isothi
• ypical color-forming compounds or couplers which areuseful in color photography, according to our inventior t, include the following:
• amylsulfanilide Z-cyanoacetylcoumarone-S-sulfon-N-n-butylanilide
• Z-cyanoacetyl-S -benzoylamino-coumarone 2-cyanoacetylcoumarone-S-sulfonclimethylamide
• amylsulfonanilide 1-p-laurylphenyl-3-methyl-5-pyrazolonc 1-B-naphthyl-B-amyl-S-pyrazolone l-p-nitrophenyl-3 -n-amyl-5-pyrazolone 1-pphenoxyphenyl-3-n-amyl-5-pyrazolone 1- henyl-3 -namyl-5-pyrazolone 1,4-phenylene bis-3-( l-phenyl-S-pyrazolone) 1 -phenyl-3-acctylamino-5 -pyrazolone 1-phenyl-3 -propionylamino-5-pyrazolone 1-phenyl-3 -n-valerylamino-5 -pyrazolone 1-phenyl-3-chloroacetylamino-S-pyrazolone 1-phenyl-3 -d ichl oro acetylamino-S-pyrazolone 1-phenyl-3 -benz
• amylacetanilide N,N'-di(w-benzoylacetyl)-p-phenylenediamine N,N'-di-(acetoacetamino)diphenyl Z-methoxyacetanilide a- ⁇ 3- a- (2,4-di-tert.-amylphenoxy) acetam1do]benzoyl sions of our invention include those described in Spenceand Carroll US. Patent 2,640,776, issued June 2, 1953;
• Example 1 A portion 'ofa gelatino-silver-bromiodide emulsion which had been sensitized with a sulfur compound and a gold salt as mentioned-above, was'coated on a cellulose acetate support and dried.- The. coating was then cut into ,several strips and one strip of each was then exposed for second to'a 500w att, 3000 K. light source on an Eastman Type II sensitomcter. One of the exposed strips was then developed for 3 minutes in adeveloper having the following composition;
• the strip was then washed for about 2 minutes in .Water and ;then given a reversal exposure for about 10 seconds (flash) with a No. 2 Photoflood set at a distance of about 60 inches.
• the strip was then developed for approximately minutes in a developer having the following formula:
• the strip was then treated for about 2 minutes in a fixing bath having the following composition:
• Thei strip was then washed in water and dried.
• the processed strip showed good definition and speed.
• Example 2 A multi-layer photographic element of the type described in Mannes et al. US. Patent 2,252,718, issued August 19, 1941, was exposed to an original multi-colored scene and developed for about 3% minutes at 80 F. in a developer having the following composition:
• the photographic element was then spray washed with Water for about 30 seconds and exposed to red illumination of about 1100 ft. candle seconds.
• the exposed material was then developed in a cyan developer having the following formula:
• the photographic element was then washed for about 30 seconds with water and exposed to blue light of 300 ft. candle seconds intensity and developed in a yellow colorproducing developer containing a phenylenediamine color developing agent, such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as Coupler No. 47 from column 4 of US. Patent 2,956,876.
• a phenylenediamine color developing agent such as 4-amino-N,N-diethylaniline hydrochloride and a yellow coupler, such as Coupler No. 47 from column 4 of US. Patent 2,956,876.
• the photographic element was then washed and fogged chemically by treatment with a sodium borohydride solution.
• the photographic element was then developed in a magenta color developer containing a color-developing agent, such as that used in Example 1 above and a magenta coupler, such as Coupler No. 30 in column 4 of U.S. Patent 2,956,876.
• the photographic element was then bleached, fixed and dried as described in Example 1.
• Example 3 Example 2 was repeated using a negative developer containing 6.0 grams per liter of l-cyclohexylamino-Z- propanol in place of the 4-aminoeyclohexanol used in Example 2. Again, there was a substantial increase in speed compared to material processed in a negative developer containing isopropylamine as the silver halide solvent.
• a photographic developing composition consisting of an aqueous alkaline solution comprising a photographic developing agent and a silver halide solvent comprising a cyclohexane containing an amino radical attached to the carbocyclic ring thereof and in addition to saidamino radical, a polar substituent selected from the class consisting of an amino radical, a hydroxyalkyl radical.
• a photographic of an aqueous alkaline solution comprising a photographic developing agent and 1,'4-bis(methylamino)cyclohexane.
• a photographic developing composition consisting of an aqueous alkaline solution comprising a photographic developing agent and 4-aminocyclohexanol.
• a photographic developing composition consisting of an aquoeus alkaline solution comprising at least one photographic developing agent selected from the class consisting ofv 3-pyrazolidones, dihydroxyben zenes and p-N- hydroxyl radical and a a developing borhfioiiidii consisting" 12.
• methylaminophenol salts and a'silver halide solvent com-- prising a cyclohexane containing an amino radical attached to the carbocyclic ring thereof and in addition to said amino radical, a polar substituent'selected from the class consisting of an amino radical, a hydroxyl radical and a hydroxyalkyl radical.
• a photographic developing composition consisting of an aqueous alkaline solution comprising at least one photographic silver halide developing agent selected from the class consisting of 3-pyrazolidones, dihydroxybenzenes and p-N-methylaminophenol salts, and 1,4-bis(methylamino)cyclohexane.
• a photographic developing composition consisting of an aqueous alkaline solution comprising at least one photographic silver halide developing agent selected from the class consisting of 3-pyrazolidones, dihydroxybenzenes and p-N-methylaminophenol salts, and 4-aminocyclohexanol.
• a photographic developing composition consisting of an aqueous alkaline solution comprising at least one photographic silver halide developing agent selected from the class consisting of 3-pyrazolidones, dihydroxybenzenes and p-N-methylaminophenol salts, and l-cyclohexylamino-2-propanol.
• a photographic developing composition consisting of an aqueous alkaline solution comprising a phenylenediamine photographic silver halide developing agent and a silver halide solvent comprising a cyclohexane containing an amino radical attached to the carbocyclic ring thereof and in addition to said amino radical, a polar substituent selected from the class consisting of an amino radical, a hydroxyl radical and a hydroxyalkyl radical.
• a photographic developing composition consisting of an aqueous alkaline solution comprising a p-N-phenylenediamine photographic silver halide developing agent and 1,4-bis(methylamino)cyclohexane.
• a photographic developing composition consisting of an aqueous alkaline solution comprising a p-phenylenediamine photographic silver halide developing agent and -1-cyclohexylamino-2-propanol.
• compositions a silverhalide solvent comprising a cyclohexane containing an amino radical attached to the carbocyclic ring thereof and in addition to said amino radical, a polar substituent selected from the class consisting of an amino radical, a hydroxyl rad ical and a hydroxyalkyl I radical.
• a process according to claim 17 wherein said silver halide solvent is 1-cyclohexylamino-2-propanol.

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Cited By (17)

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  • BE BE623790D patent/BE623790A/xx unknown
• 1961
  • 1961-10-23 US US147055A patent/US3128182A/en not_active Expired - Lifetime
• 1962
  • 1962-10-06 DE DEP1269A patent/DE1269484B/de active Pending
  • 1962-10-23 GB GB40182/62A patent/GB1024612A/en not_active Expired

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